Alkylolamine derivatives of aliphatic acids



Patented Feb. 6, 1934 STAT-Es '1' v err-Ice DERIVATIVES OF ALIPHATIC ACIDS Jean Georges Kern,

J. Sala, Wilmington, Pont de Nemours &

Waltham, Mass., and Charles DeL, assignors to E. I. du

Company, Wilmington,

Del, a corporation of Delaware No Drawing. Original Serial No. 210,714.

application August 4,1927, Divided and this application March 21, 1930. Serial No. 437,938

8 Claims. ((31. 260112) and to the sulfonic acid derivatives of these acids and more particularly to the ethanolamine salts of the higher fatty acids.

This invention has as objects the preparation of soluble oils, solvents and detergents as well as of antiseptic soaps.

These objects are accomplished by making the salts of the bases known as alkylolamines or hydroxy-alkylamines, more particularly of the ethanolamines, by combination with the'fatty acids mentioned above by any of the well known methods for the production of salts.

The bases used for our purposemay be represented by the following general formula:

where Alla represents an aliphatic or hydroxy aliphatic radical, R1 and R2 represent hydrogen or an aliphatic radical or a hydroxraliphatlc radical or a poly hydroxy aliphatic radicalglnw making these new soluble oils we may proceed as follows:

The free fatty acids are combined directly with an organic base or a mixture of such bases. If the fatty acid is a solid the preparation is aided by the application of heat. It is also possible to start from the glycerides of the fatty acids, i. e., olive oil, cottonseed oil, castor oil, linseed oil and the like by saponifying the glycerides by heating with the base to a high-temperature. In this case we find that the reaction is complete when a sample of the mixture dissolves entirely in water. If water is present at the start this may be driven oil, the base not being volatile, until a concentrated product is left behind. When making these products by this method it is found that an excess of base is necessary to give the most satisfactory results.

-When preparing the products obtained from the sulionated fatty acids we may proceed as follows:

The acid product of the mixture of the Sill-- fonated unsaturated acid as obtained by the action of sulfuric acid on an unsaturated oil such as castor oil in the well known manner is freed of mineral acid by washing. It is then freed of water either by settling or by any other suitable means and then enough of the alkylolamine base is added at ordinary temperature to neutralize the acidity of the sulfonic acid group or of both sulfonic acid and the carboxylic acid groups.

The following examples will serve to illustrate our method of procedure, but it is to beunderstood that the invention is not to be. limited thereby:

Example 1 2823.7parts of free oleic acid are mixed with 1490 parts of tri-ethanolamine.

Example 2 semi-solids, particularly, water soluble and ready for use without further treatment.. It is possible that the resultant material may of the base with the oleic acid but this has not been definitely established and is,'in fact, immaterial to the success of the invention.

Example 3 298.37 parts of ricinoleic acid CnHMOI-I) 0001-! are mixed with r 105 parts di-ethanolamine. The resultant product is a clear yellow oil, very soluble in water.

Example 4 Example 5 284.39 parts of she the melt are stirred be a compound heated on the water bath ric acid are melted. Into 149 parts tri-ethanolamine,-stirring is continued at a temperature of about at 0. until the mixture is uniform. s The resultant product on cooling is a solid, not

very soluble in water but very soluble in alcohol.

It acts as an excellent assistant in promoting solution.

Example 6 solution is cloudy but becomes clear on the addition of some excess base, e. g. to

, Example 7 282 parts oleic acid are caused to react as given in theabove example with 119 parts of methyl di-ethanolamine cm-N=(cH=-cmom= The soap obtained in this way has the property,

when in alcoholic solution, of dissolving mercuric oxide and giving a relatively stable product soluble in water. This is altogether a surprising resuit and illustrates the use of these new soaps for pharmaceutical purposes.

Example 8 6 parts of a crude sulfonated-oil made by the action of sulfuric acid on castor oil are mixed with 1 part of mono-ethanolamine.

Example 9 2.7 parts of a crude sulfonated oil mixture in the form of free acids are mixed with 1 part of a mixture of diand tri-ethanolamine. The products of Examples 8 and 9 are entirely soluble in water. They are thick yellow oils presumably containing salts of the bases of the sulfonic acids but this point has not been definitely established and is immaterial to the success of the invention. The products formed in this way are quite satisfactory for ordinary purpom.

In dyeing Ponsol Blue GDdouble paste, Schultz- No. 842, on cotton yarn in the package machine, using 5% of color 2%% sodium hydroxide 3% 'hydro'sulflte. the addition of 1% of the product formed by combining 1 mole of sulfo-ricinoleic acid and 1 mole tri-ethanolamine,- containing di-ethanolamine.

- results in a brighter, more level dyeing.

Example 10 If a pure product is needed theoperation may be carried out as follows: 1

I 378 parts of pure sulfo-ricinoleic' acid prepared by the action of chloro-suli'onic acid on pure. ricinoleic acid are mixed with 149 parts of tri-ethanolamine. s

In the above case the addition of a further molecular-equivalent bf base produces a more soluble oil. The reason may be that the extra quantity of base .combines with the carboxyl group but again this point'has not been deter-, mined.

In the above examples any one of the'bases as defined by the general formula given above may stances than do ordinary soaps. detergent property of soapswithout the high al- -cnH2n-1 (OH) 2.

We have found that these products, which are essentially organic soaps possess a greater dissolv- DB' power or dispersing power for organic subkalinity characteristic of sodium or potassium They possessthesalts of the fatty acids. These products forvthese reasons have a distinct advantage for many Durposes and particularly as assistants in dyeing,and

those compounds which are derived from sulfonated caster-oil, by the process mentioned are in many wayssuperior to ordinary sulfonated oils. Their superiority is evidenced by the greater evenness of the shades developed, the better utilization of the color, and the greater brilliance of the dyeing.

tion of insoluble organic bases such as aminoazo-benzene, paraenitro-benzene, azc-diphenylamine, benzeneazo-naphthalene-azo-phenol, rosanthrene base, di-ethvl-para-amido-phenol-lzt naphtho-quinone-mono-imide. 2.4 di-nitro-benzene-I-azo-dkethyl-anilim, etc. It takes about 2 to 5 parts of the solvent for 1 part of the insoluble base. These solutions may be used very successfully for the purpose of dyeing fibers of ester- 1 ifled cellulose.

It has also been found that these soaps dissolve metallic hydroxides and oxides. for example, mercuric oxide, and this property indicates their probable value in pharmacol gy, for example, in the production of antiseptic soaps and the like.

As many apparently widely diiferent embodiments of this invention may be made without departing from the spirit thereof, it is to be understood that we do not intend to limit ourselves to When added to water they bring about solution or dispersion in so fine a form as to appear a soluthe specific embodiments thereof except as indicated in the appended claims.

-We claim:

. 1. A product resulting from the chemical combination of oleic acid and an alkylolamine containing a plurality of alkyl groups. 2. ,A product resulting from the chemical combination of oleic acid and an ethanolamine containinga. plurality of ethyl groups.

3. A product resulting from the chemical combination of oleic acid and at least one of the substances consisting of di-ethanolamine and triethanolamine. v

4. A product resulting from the chemical combination of oleicacid and one of the amines from the group .consisting of di-etha'nolamine, triethanolami'ne and amino-propane dioi.

- 5. A product resulting from the chemical combination of oleic acid and 'di-ethanolamine.

8. A product resulting from the chemical combination of oleic "acid and a mixture of diand tri-ethanolamines. l

z. A product resulting from the chemical combination-of oleic acid and tri-ethanolamine bination of oleic acid and amino-propane dioi. JEAN GEORGES KERN. CHARLES J. BALA.

a. A product resulting from the chemical ccm- 

